Method of preparing copper arsenicals



V Patented Nov. 6, 15345 v I UNITED STATES PATENT v "F F ICE:

METHOD or'rREPARING COPPER ARSENICALS George'W. Pearce and Alfred W. Avens,

V Geneva, Ni -Y. I N'ofDr'awing. Original applicationJune 13, 1940,

serial No. 341,179. Divided-and this applica tion Auguste; 1943, Serial No. 497,969

3 Claims, (01. 23-53) This is a division of application Serial No; instead of arsenic acid. We will now describe 341,179, filed June 18, 1940, 'forArsriical insectispecifically the use of dical'cium arsenate'i'n the cities", issued March 21',- 1944; as :Patent No. preparation of copper calcium arsenate suitable 2,344,895. The cla'lms in that case are directed for use as an insecticide. particularly to basicca'lcium arsenate; the claims 5 When arse'nical sprays-are used on plant foliage, in the present ease are directed particularly to arsenica-l injury-to the foliage-and the fruit frebasi-c'ccpper arse-hate; and-inacompanion diviquently results. To avoid this dificulty, copper 'sional applicationfiled' cotemporaneouslyhereand some of its compounds'can act as arsenical with the claims are directed to zinc calcium injury correc'tives or preventatives when used in arsenate. Thepresent invention relates to insecan insecticidal spray or dust mixture. Weak ticides' and fungicides of the arsenic type, and its Bor ea x mixture for ex mp e h -r r0 e principal object is :broadly to provide a-co'mmereflicient in this capacity. We have found that cial method of producing arsenicals of definite if one-treats dicalcium arsenate, itself a very toxic chemicalcompositionso asto haveconsistent and substance to plant foliage, with copper or various easily reproducible roperties. Various specific compounds of copper, a highly insoluble copper objects will -be'come apparent a -the description calciumarsenical is obtained which is substan proceeds. 'Wl-iil'e arsenic'has long been recognized tiall y safe to foliage. When insoluble copper as a use'iuleconomi'c poisom-the chief problem e materials are used to combine with diin its use as an insecticide has been the difficulty calcium 'arsenate, it is best to mix the reactants in standardizing the commercial products emintimately in-a dry state and subject the mixture played; due to the fact that they n rall i re-an autoclaving operation for .about'2 hours at volved mixtures of various arsenical compounds q- Ste'am pressure p ds having different chemical and physical proper- D in0h)- A5 a further illustration of he ties. While considerable improvements have been principles indicated above, We have heat treated made in such commercial arsenicals, they have (110810111111 a t in the presence of the rep continued to produce inconsistent behavior with Sentatilc materials given n a e n each respect to insect toxicity and plant injury T instance a reaction proceeds in which the dicaldifiiculty appears to b du t th fact; t t in cium arsenate is converted to a more insoluble most prior processes it a practically impossible arsenate suitable for insecticidal and in some to obtain anything but mixtures of two or more instances also fungicidal purposesspecies of arsenates. These prior processes started with arsenic acids and generally ended Table 1 up with mixtures, instead of a definite compound. P t f ar 0 [Th6 0P1? lmpm lnt Q' p 1n the commel' c1311 dioalc ium Parts of reacting material insecticide field 1s di-lead arsenate, which is a arsenate compound of definite composition, generally produced from litharge and arsenic acid, using acetic flipper (Name/red metal)- acid as a catalyst. Lead however has many ob- 1 igfigii x ifi e i v fifi ectionable qualities, particularly where the production of food is concerned. Unfortunately, 40 arsenates of other more desirable metals cannot The Various *treatments indicated in Table 1 be produced by the Same typ of reaction that were carried out by intimately mixing the dicalproduces diqead arsenate cium arsenate with the various materials shown By the invention described in the application d then autoclaving the mixture with Steam for f which this is a division it is possible to 2 hours at 10-15 kgs. per sq. cm. The reacting merciany produce a single defi it Species of materials were added in excess over that required cium senate, namely basic calcium arsenate, to displace all the hydrogen present in the dicaland by the present invention it is possible to procium arsenate- In gener all when dicalcium arseduce either coppe calcium arsenate or basic nate is treated with metals or their oxides the copper arsenate, though the processes are enprimary reaction appears to be displacement of tirely different from the previous lead method the hydrogen and formation of a u e salt. above mentioned. The processes difier funda- On h h r h n i a ed with u s,

mentally from the prior processes in that they chlorides, nitrates and other salts or compounds use dicalcium arsenate as the starting material, of metals, the reaction may result in displacement cidal and fungicidal properties. The following procedure results in a very pure basic copper arsenate (Cu(CuO)AsO4).

Five (5) parts of powdered dicalcium arsenate are suspended in 100 parts of water and 2 parts i of copper in the form of copper nitrate dissolved in about 5 parts of water are added. The mixture is heated to boiling and stirred for about one-half hour. The precipitate first formed in the mixture is a voluminous hydrated mass and On heating tends to dehydrate and become crystalline. The product is filtered ofi, dried and ground. The analysis will be very close to the theoryfor basic copper arsenate (Cu(CuO)AsO4).

It will be evident from the foregoing that the use of dicalcium arsenate in place of the usual arsenic bearing starting materials makes possible the production of various arsenical preparations having consistent and easily reproducible properties. While dicalcium arsenate does not appear to be commercially available at the present time, it is easily and cheaply prepared on a commercial scale if desired by several methods, more or less well known, some of which are reviewed in the parent application of which this is a division,

and it is not necessary to repeat them here. Moreover, since the anhydrous form (CaHAsOO of dicalcium arsenate as well as the completely dehydrated form known as calcium pyroarsenate (CELZAS207) are readily returned to the monohydrated or other hydrated forms of dicalcium arsenate, it will be understood that the process includes the use or these other forms for the manufacture of arsenicals. The arsenicals described are particularly useful in controlling insect pests of plants, but it will of course be understood that they may also be used for any other purposes to which they are suited,

While in the foregoing we have given specific examples of the type of process, it will be understood that it is merely by way of illustration to make clear the principles of the invention, which is not limited to the particular examples shown, but is susceptible to various modifications and adaptations in different instances as will be apparent to those skilled in the art, without departing from the scope of the invention as stated in the following claims.

We claim:

1, The method of preparing copper arsenicals of definite composition, which consists in taking solid dicalciumarsenate, mixing it with copper bearing material in excess, and heating the mixture to a temperature at which the reacting materials react to form a copper arsenical compound.

2. The method of preparing copper calcium arsenate, which consists in taking solid powdered dicalcium arsenate intimately mixed with copper bearing material in excess selected from the group consisting of solid powdered copper and its oxides, and heating the mixture to a temperature at which the reacting materials react to form copper calcium arsenate.

3. The method of preparing basic copper arsenate, which consists in taking dicalcium arsenate and boiling it in a solution of a copper salt, the anion of which reacts with the calcium of the dicalcium arsenate to form a soluble calcium compound, and separating and drying the basic copper arsenate.

GEORGE W. PEARCE. AII 'RED W. AVENS. 

